Diamino-s-triazines

ABSTRACT

Valuable new triazine derivatives having good herbicidal properties, especially for controlling unwanted plants without damaging crop plants.

United States Patent Koenig et al. 1451 July 25, 1972 54 DIAMINO-S-TRIAZINES [56] References Cited UNITED STATES PATENTS [72] 1mm": i 5:? a 3,185,561 5/1965 Acker ..260/249.8X 5 2 f A 3,235,359 2/1966 Ackcr ...260/249.8 x mm 3,261,835 7/1966 l-lamm 61311... ..260/249 3 fl'f' 3'33??? 341323 -Li""' i 523313 8 1? pezl ee many Ludw' 3,306,725 2/1967 Knuslietal. ...260/249 8 x 3,347,657 10/1967 Knuslietal. ..260/249.8X [22] Filed: Nov. 21, 1968 Primary Examiner-John M. Ford [21] APPI'NO" 777873 Attorney-Manall,.lohnston,Cook&Root

521 US. Cl ..26o/249.a,71/93, 260/2499 [571 ABSTRACT C0711 55/20 Valuable new triazine derivatives having good herbicidal pro- [58] Fieldof Search ..260/249.8;7 1/93 perties, especially for controlling unwanted plants without damaging crop plants.

3 No Drawings DIAMINO-S-TRIAZINES The present invention relates to valuable new triazine derivatives which have a strong herbicidal action and a process for controlling unwanted plants without damaging crop plants with these triazine derivatives.

It is known to use 2,4,6-substituted triazines, especially 2- chloro-4,6-bis-(ethy1amino)-s-triazine, as herbicidal active ingredients; however, their action is unsatisfactory.

An object of the invention is valuable new triazine derivatives. A further object of the invention is valuable new triazine derivatives containing an alkyl radical substituted by oxygen or sulfur. Yet another object of the invention is a process for controlling unwanted plants with valuable new triazine derivatives without damaging crop plants.

These and other objects of the invention are achieved by triazine derivatives having the general formula NH-R in which R denotes a chlorine or bromine atom or a cyano, methoxy or thiomethyl group. R denotes a lower aliphatic or alkoxyalkyl radical having not more than six carbon atoms or a lower alkylthioalkyl radical and R denotes a lower alkylthioalkyl radical or a lower alkoxyalkyl radical or a chlorine atom. These substituted triazines have not previously been described in the literature.

The compounds may be prepared stepwise at different temperatures for example by reaction of cyanuric chloride or cyanuric bromide with the corresponding amines in the presence of agents which bind hydrogen halides. If desired, the third halogen atom in the triazine may be exchanged, for example by reaction with sodium methylate, sodium methylmercaptide or sodium cyanide.

90 parts by weight'of ethylamine is dripped, at a temperature of to C, into a solution of 189 parts by weight of cyanuric chloride in 600 parts by weight of acetone. The reaction mixture is then stirred for one hour at 10 to 20 C, the precipitated ethylamine hydrochloride is suction filtered and the filtrate is freed from solvent in vacuo. The crystalline residue is recrystallized from cyclohexane. 189 parts by weight of 2,4-dichloro-6-ethylamino-1,3,5-triazine is obtained, boiling point 103 to 105 C.

From two dropping funnels 13.2 parts by weight of amethylB-methoxyethylamine and a solution of 6 parts by weight of sodium hydroxide in 20 parts by weight of water are simultaneously added, at a temperature of 20 to 30 C, to a solution of 29 parts by weight of 2,4-dichloro-6-ethylaminol,3,5-triazine in 200 parts by weight of acetone. The whole is then stirred for a fairly long time at room temperature (20 C), the reaction mixture is filtered and the filtrate freed from solvent in vacuo. The crystalline residue is recrystallized from cyclohexane. 24 parts by weight of 2-chloro-4-ethylamino-6- (a-methyl-B-methoxyethyl)-amino-1,3,5-triazine, boiling point 96 C, is obtained.

Some of the active ingredients according to the invention are listed below:

2chloro-4-isopropylamino-6-(a-methyl-B-methoxyethyl)- amino-1,3,5-triazine, b.p. 124 to 125 C; 2-thiomethyl-4-ethylamino-6-(B-methylthioethyl)-amino- 1,3,5-triazine, b.p. 109 to 1 10 C. 2-(a-methyl-B-methoxyethyl)-amino-4-(a-methoxypropyl)- amino--chloro-s-triazine, b.p. 76 to 78 C; 2-( a-methyl-B-methoxyethyl )-amino-4-( a-methoxypropyl amino-fi-methoxy-s-triazine, b.p. (0.05 mml-lg) 186 to 1 89 C; 2-(a-methyl-fl-methoxyethyl)-amino-4-ethylamino-6- thiomethyl-s-tri-azine, b.p. (0.1 mmHg) 162 C; 2-(a-methyl-B-methoxyethyl)amino-4-(a-methoxypropyl)- amino-6-thio-methyl-s-triazine, b.p. (0.08 mml-lg) 191 to 193 C; 2,4-bis-(a-methyl-B-methoxyethyl)-amino-6-methoxy-striazine, b.p. (0.1 mml-lg) 181 to 184 C; 2,4-bis-(a-rnethyl-B-methoxyethyl)-amino-6-chloro-striazine, b.p. (0.01 mmHg) 178 to 180 C; 2,4-bis-(a-methyl-B-methoxyethyl)-amino-6-thiomethyl-striazine, b.p. (0.5 mmHg) 197 to 201 C;

2-( a-methyl-B-methoxyethyl )-amino-4-ethy1amino-6- methoxy-s-triazine; b.p. (0.4 mmHg) 168 to 170 C; 2-(a-methyl-B-methoxyethyl)-amino-4-methylamino-6r thiomethyl-s-tri-azine, b.p. (0.2 mmHg) 173 to 175 C; 2-(a-methyl-fi-methoxyethyl)-amino-4-isopropylamino-6- methoxy-s-tri-azine, b.p. (0.2 mmHg) 148 to 150 C;

YW N N Y R R R B.P., C. 13.1. (mm. Hg)

Cl CH: NH-CH2-CH2SCH3 65-67 NH-CH O CzHs C1 NH-CzHs CH3 67-68 NH--CH O-C2H5 Cl CH3 CH NH-CH OC2Hs NH--CH O-CzH5 CH2 CH Cl NH-CH: CH3 97-98 NH-CH O-CzHs 1 CH3 NH-CHr CHz-CHzO-CH3 NH-CH 0-C H5 Cl CH CH 88-89 NIICH NH-CH 0-C3H1 CH: CH:

R! R R B.P., 0. B.P. (mm. Hg) or NH- oHrcHrcm-o-cm on, 66-71 NH-CH s-cH;

C1 NH-CHz-CHz-CHrO-CH: CH5

NHCH O-C2Hs 0H;- s H/RH; NH-CHPCHz-CHz-O-CII;

N H-C 0CH3 H.

CH S- NH-CHZ-CHZ S -C2Hs NH- 3- (3112-- 5 Cr 83 113;- 1 lg)- Further active ingredients are named in the Examples. EXAMPLE 2 As herbicides, the new compounds may be applied as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the compounds are being used; in any case, it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, mineral oil fractions having medium to high boiling points, such as kerosene or diesel oil, coal-tar oils and oils of vegetable or mineral origin, and also cyclic hydrocarbons such as tetrahydronaphthalene and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions, the ingredients as such or dissolved in a solvent may be homogenized in water by means of wetting or dispersing agents (e.g. polyethylene oxide adducts). Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e. g. clay, diatornite or fertilizers.

The following Examples demonstrate the superiority of the compositions according to this invention over known active ingredients.

EXAMPLE 1 Plastic pots having a diameter of 8 cm are filled with loamy sandy soil in a greenhouse and sown with seeds of barley (Hordeum vulgare), wheat (Triticum sativum), Indian corn (Zea mays), annual meadow grass (Poa annua), slender foxtail (Alopecurus myosuroides), small nettle (Urtica urens), wild mustard (Sinapis arvensis), white goosefoot (Chenopodium album), vetch (Vicia sp.), chamomile (Matricaria chamomilla) and chickweed (Stellaria media); the soil prepared in this manner is then treated with 1.5 kg per hectare of 2-chloro-4- ethylamino-6-(a-methyl-fl-methoxyethyD-amino-1,3,5- triazine (I) and, for comparison, with 1.5 kg per hectare of 2- chloro-4,6-bis-(ethyl-amino)-s-triazine (ll), these amounts of the active ingredients each being dispersed in 500 liters of water. After four to five weeks I shows superior compatibility with barley (Hordeum vulgare) and wheat (Triticum sativum) and also exhibits a stronger herbicidal action on weeds.

The results of the experiment may be seen from the following table:

Acitive ingrefilient barley l0 wheat 10 Indian com 0-l0 0-10 annual meadow grass 90 80 slender foxtail 80 70 small nettle I00 90-100 wild mustard 1 90 white goosefoot 90-100 80-90 vetch 90-100 80 chamomile 90 80-90 chickweed 90-l00 80-90 0 no damage 100 total destruction triazine (I) and, for comparison, with 1.5 kg per hectare of the active ingredient 2-chloro-4,6-bis-(ethylamino)-s-triazine (ll),

each amount of the active ingredients being dispersed in 500 liters of water. After three weeks it is ascertained that I shows superior compatibility with barley (l-lordeum vulgare) and wheat (Triticum sativum) and also exhibits a stronger herbicidal efl'ect on weeds. 7

' The results of the experiment maybe seen from the following table:

Active ingredient I II barley 0-l0 20-30 wheat 10 20-30 Indian com 0 0-l0 wild mrutard 100 90400 small nettle 90-100 90-l00 white goosefoot 90-100 90-100 chamomile 90 -90 chickweed -100 90 annual meadow grass 90-100 90 slender foxtail 90 80 0 no damage I00 =total destruction EXAMPLE 3 In a greenhouse, seeds of wild mustard (Sinapis arvensis), small nettle (Urtica urens), white goosefoot (Chenopodium album), chamomile (Matricaria chamomilla), chickweed (Stellaria media), annual meadow grass (Poa annua) and slender foxtail (Alopecurus myosuroides) are sown in loamy sandy soil; the soil prepared in this manner is then treated with 5kg per hectare of 2-chloro-4-ethylamino-6-(a-methyl-flmethoxyethyl)-arnino-l,3,5-triazine (l) and, for comparison, with 5kg per hectare of 2-chloro-4,6-bis-(ethylamino)-l,3,5- triazine (ll), each amount of the active ingredients being dispersed in 500 liters of water per hectare. After four to five weeks it is ascertained that I has a stronger herbicidal action than ll. v

EXAMPLE 4 The plants wild mustard (Sinapis arvensis), small nettle (Urtica urens), white goosefoot (Chenopodium album), chamomile (Matricaria chamomilla), chickweed (Stellaria media), annual meadow grass (Poa annua) and slender foxtail (Alopecurus myosuroides), growing on an experimental area, are treated at a growth height of 3 to 12 cm with 5kg per hectare of 2-chloro4-ethylamino-6-(a-methyl-B-methoxyethyl)- amino-l,3,5-triazine (I) and, for comparison, with 5kg per hectare of 2-chloro-4,6-bis-(ethylamino)-l,3,5-triazine ll), these amounts of the active ingredients each being dispersed in 500 liters of water per hectare. After one to two weeks it is ascertained that 1 acts more quickly on the above-mentioned weeds and weed grasses than 11, and after four to eight weeks all the plants are almost completely withered.

The following substances have the same biological action as l in Examples 1,2,3 and 4:

2-chloro-4-isopropylamino-6-(a-methyl-fl-methoxyethyl)- amino-1,3,5-triazine, 2-thiomethyl-4-isopropylamino-6-(a-methyl-fi-methoxyethyl)-amino-l ,3,5-triazine,

2-methoxy-4-isopropylamino-6-(a-methyl-B-methoxyethyl)-amino-l ,3,5-triazine, 2-chloro-4-tertiary-butylamino-6-(a-methyl-B-methoxyethyl)-amino-l ,3,5-triazine, 2-chloro-4,6-bis-( a-methyl-fi-methoxyethyl )-amino- I ,3,5-

.triazine, 2-chloro4-methylamino-6-(a-methyl-B-methoxyethyl)- amino-l ,3,5-tri-azine, 2-bromo-4-ethylamino-6-( a-methyl-B-methoxyethyl)- amino-1,3,5-tri-azine, 2-cyano-4-ethylamino-6-( a-methyl-B-methoxyethyl)- amino-1,3,5-triazine,

2-chloro-4-methoxyethylamino-6-( a-methyl-B-methoxyethyl)-amino.-l ,3 ,S-triazine, 2-chloro-4-y-methoxypropylamino-6-(a-methyl-B-methoxyethyl)-amino-l ,3,5-triazine, 2-methoxy-4-ethylamino-6-(a-methyl-B-methoxyethyl)- amino- 1,3,5-triazine, I '2-thiomethyl-4-ethylamino-6-(a-methyl-B-methoxyethyl)- amino-1,3,5-triazine.

EXAMPLE 5 PLastic pots having a diameter of 8 cm are filled with loamy sandy soil in a greenhouse and then sown with seeds of barley (Hordeum vulgare), wheat (Triticum sativum), annual meadow grass (Poa annua), white goosefoot (Chenopodium album), wild mustard (Sinapis arvensis), small nettle (Urtica urens), chickweed (Stellaria media) and chamomile (Matricaria chamomilla) and treated the same day with 2 kg per hectare of 2-thiomethyl-4-ethylaniino-6-(B- methylthioethyl)-amino-l,3,5-triazine (l) and, for comparison, with 2 kg per hectare of 2-chloro-4,6-bis- (ethylamino)-l,3,5-triazine (11), these amounts of the active ingredients each being dispersed in 500 liters of water. After four to five weeks it is ascertained that the broadleaved and grassyweeds are almost completely withered but that I, in comparison to II, has superior compatibility with the crop plants wheat (Triticum sativum) and barley (l-lordeum vulgare).

EXAMPLE 6 In a greenhouse the plants barley (Hordeum vulgare),

wheat (Triticum sativum), Indian corn (Zea mays), annual meadow grass (Poa annua), slender foxtail (Alopecurus myosuroides), wild mustard (Sinapis arvensis), white goosefoot Chenopodium album), small nettle (Urtica urens), chickweed (Stellaria media) and chamomile(Matricaria chamomilla) are Active ingredient 1 ll barley 0-10 20-30 wheat 10 20-30 Indian corn 0-10 0-10 annual meadow grass 90-100 90 slender foxtail 90 80 wild mustard 100 90-100 White goosefoot 100 90-100 small nettle 90-100 90-100 chickweed 90-100 90 chamomile 90-100 80-90 0 no damage, 100 total destruction EXAMPLE 7 An experimental area is sown with annual meadow grass (Poa annua), slender foxtail (Alopecurus myosuroides), wild mustard (Sinapis arvensis), white goosefoot (Chenopodium album), small nettle (Urtica urens), chicltweed (Stellaria media) and chamomile (Matricaria chamomilla) and sprayed the same day with 5kg per hectare of 2-thiomethyl-4- ethylamino-6-( fi-methylthioethyl )-amino-l 3 ,5-tri azine, dispersed in 500 liters of water per hectare. After four to five weeks it is ascertained that all the plants are withered.

EXAMPLE 8 The plants annual meadow grass (Poa annua), slender foxtail (Alopecurus'myosuroides), wild mustard (Sinapis arvensis), white goosefoot (Chenopodium album), small nettle (Urtica urens), chickweed (Stellaria media) and chamomile (Matricaria chamomilla). growing on experimental area, are sprayed at a growth height of 3 to 18 cm with 5kg per hectare of 2-thiomethyl-4-ethylamino-6-(B-methylthio-ethyl)-amino- 1,3,5-triazine (I), and, for comparison, with 5 kg per hectare of 2-chloro-4,6-bis-(ethylamino)-l ,3,5-triazine (11), these amounts of the active ingredients each being dispersed in 500 liters of water per hectare. After eight to 10 days it is ascertained that more damage has been caused to the broadleaved and grassy weeds treated with 1 than to those plants treated with 11. After three to four weeks almost all the plants are completely withered.

The following substances have the I in Examples 5,6,7 and 8: 1

2-thiomethyl-4-isopropylamino-o-(fl-methylthioethyl)- amino-1,3,5-triazine, 4 J 2-chloro-4-ethylamino-6-(fl-methylthioethyl)-amino-l ,3',5-

triazine,

2-chloro-4-isopropylamino-6-(B-methylthioethyl)-amino--v I 1,3,5-triazine, 2-cyano-4-isopropylamino-6-( B-methylthioethyl )-amino- 1,3,5-triazine, 2-chloro-4-methylamino-6-(fi-methylthioethyl)-amino- 1,3,5-triazine.

EXAMPLE 9 mustard (Sinapis arvensis), vetch (Vicia sp.), chamomile (Matricaria chamomilla) and chickweed (Stellaria media);

' the soil is then treated with 1.5kg per hectare of 2-ethylamino- 4-propoxyisopropylamino-6-chloro-s-triazine (l), 1.5kg per hectare of 2-isopropylamino-4-propoxyisopropylamino-6-.

chloro-s-triazine (ll), 1.5kg per hectare of 2'-isopropylamino- 4-propoxyiso-propylarnino-fi-methoxy-s-triazine (III), l.5kg per hectare of 2-ethylamino-4-propoxyisopropylamino-6-' methoxy-s-tn'azine (IV), 1.5kg per hectare of 2,4-bis-(ethoxyisopropylamino)-6 methylmercapto-s-triazine (V) and l.5 kg per hectare 3 of 2-ethylamino-4-ethylmercaptoisopropylarnino-6-chloro-s-triazine (VI), these amounts of the 7 active ingredients each being dispersed in 500 liters of water per hectare. The results of the experiment after four to five weeks may be seen from the following table:

Active ingredient I II III IV V VI Indian corn 0-10 0-10 0 0 0-10 0-10 barley 10 0-10 0-10 0-10 O-lO 0-10 wheat 10 0-10 0-10 10 0-10 O-lO annual meadow grass -90 80 80 8O 8O 80 same biological action as slender foxtail 80 small nettle 90-100 In a greenhouse the plants barley (Hordeum vulgare), wheat (Triticum sativum), lndian corn (Zea mays), small nettle (Urtica urens), white goosefoot (Chenopodium album), chamomile (Matricaria chamomilla), chickweed (Stellaria media), annual meadow grass (Poa annua), and slender foxtail (Alopecurus myosuroides) are treated at a growth height of 2.5 to 16 cm with 1.5kg per hectare of 2-ethylamino-4- propoxyisopropylamino--chloro-s-triazine (1), 1.5kg per hectare of Z-isopropylamino-4-propoxyisopropylamino-6-chloros-triazine (ll), 1.5kg per hectare of 2-isopropylamino-4- propoxyisopropylamino-o-methoxy s-triazine (Ill) and 1.5 kg per hectare of 2,4-bis-(ethoxyisopropylamino)-6-methylmercapto-s-triazine (1V), these amounts of the active ingredients each being dispersed in 500 liters of water. The results of the experiment after three weeks may be seen from the following table:

Active ingredient 1 ll 111 IV barley -10 0-10 040 wheat O-lO 0-10 0-10 0-10 Indian corn l0 0 10-20 I0 small nettle -100 90-l00 90-100 90-100 white goosefoot 90-100 90-100 90-l00 90-100 chamomile 90-100 90-100 90-100 90-100 chickweed 90-100 90-100 90-100 annual meadow grass 90-100 90-100 100 90-100 slender foxtail 90-100 90- l ()0 90- I00 90-100 0 no damage 100 total destruction We claim: 1. A compound of the formula in which R denotes a chlorine or bromine atom, R denotes a lower alkyl radical or an alkoxyalkyl radical having at most six carbon atoms or a alkylthioalkyl radical having at most 6 carbon atoms, and R denotes a lower alkylthioalkyl radical or a a I W8? I 2 UNITED STATES" PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5, 79, 7 D'ated July 5, 97

Inventofls) I Karl-Heihz Koehig; Artur Maachke and Adolf Fischer It is oer t ified that: error appears in the above-identified patent and that said Lettersf Patent are hereby corrected as shown below:

First page, left-hand column, insert Q Q Foreign Application Priority Data NOV.- 28, 1967 Germany. .P 16 70 289.9

Column 5,. in the table,- under "R2", third formula down, that portion of the formula reading "EH should read CH Column 6, line 21, "(Urtioa u-rnes)" should read (Urticd urens) Signedand sealed this 2nd day of Jariuary 1973.

(SEAL) Attest:

EDWARD M. PLETCHER,JR. v ROBERT GOTTSCHALK Commissioner of Patents Attesting Officer 

2. 2-chloro-4-ethylamino-6-( Alpha -methyl- Beta -methoxyethyl)-amino-1,3,5-triazine.
 3. 2-chloro-4-isopropylamino-6-( Alpha -methyl- Beta -methoxyethyl)-amino-1,3,5-triazine. 